Hydrocarbonaceous-oil shale composition

ABSTRACT

The hydrocarbonaceous substance, e.g., a petroleum asphalt cement such as a residual, pitch, Trinidad asphalt, etc., is composited with an oil shale which has been ground to an average particle size of less than about 75 microns and then eminently admixed with the hydrocarbonaceous material at a temperature in the approximate range 250*-375*F.

United States Patent [1 1 [111 3,902,914 Gagle et a1. Sept. 2, 1975 [54]HYDROCARBONACEOUS-OIL SHALE 1,649,545 11/1927 Re nou 106/284 2,1 13,7944/1938 Leaut 106/284 3,072,593 1/1963 Marx et al 106/281 X [75]Inventors: Duane W. Gagle; Homer L. Draper,

b th fB rt] '11 ,Okl.

O 0 a e a Primary Examiner-Joseph L. Schofer Assigneel PhillipsPetroleum p y Assistant Examiner Herbert J. Lilling Bartlesville, Okla.

[22] Filed: Mar. 9, 1973 [57] ABSTRACT 21 A l. N 339,536 1 pp 0 Thehydrocarbonaceous substance, e.g., a petroleum asphalt cement such as aresidual, pitch, Trinidad as- 106/281; 106/284 phalt, etc., iscomposited with an oil shale which has C081! C09d been ground to anaverage particle size of less than [58] Fi ld Of ar 284 about 75 micronsand then eminently admixed with the hydrocarbonaceous material at atemperature in [56] Referen Cited the approximate range 250375F. UNITEDSTATES PATENTS 1,643,520 9/1927 Reeve 106/284 9 DrawmgsHYDROCARBONACEOUS-OIL SHALE COMPOSITION The invention herein describedwas made in the course of or under a contract or subcontract thereunder,(or grant) with the Department of the Air Force.

This invention relates to a hydrocarbonaceous composition. Moreparticularly, it relates to a composition of a hydrocarbonaceousmaterial and oil shale. Still more particularly, the invention relatesto the compositing even without a solvent of a hydrocarbonaceousmaterial e.g. a petroleum asphalt cement and the like with a finelydivided or ground oil shale, the average particle size of which ismeasured in microns. the invention also relates to a method ofcompositing a hydrocarbonaceous material with a finely subdivided oilshale.

In one of its concepts, the invention provides an im provedhydrocarbonaceous substance having better aging, plasticity, coveringand adhesion properties than the original hydrocarbonaceous substancefrom which it is produced, the composition containing composited withthe hydrocarbonaceous substance, a finely subdivided oil shale. inanother of its concepts, the invention relates to a method forcompositing a carbonaceous substance, as herein defined, with a finelysubdivided oil shale, also as herein defined, to produce a compositionhaving desirable aging, plasticity, covering and adhesion properties.

The compositions of the invention are particularly well suited forapplications including among others, a pavement binder, roofingasphalts, tiles, mastics, etc.

US. Pat. No. 3,072,593 issued Jan. 8, [963, describes and claims aprocess of making molded articles which consists essentially ofintimately admixing oil shale, containing at least about gallons ofrecoverable oil per ton of oil shale, and a solid polymer of amono-l-olefin and subjecting said mixture to molding pressure at amolding temperature in the range of about 250 to about 4()0F.Compositions and articles of manufacture are also claimed.

We have now discovered that oil shale, quite finely ground intoparticles which are substantially all of them less than 75 micron insize is a superior mineral filler product for asphalt, coal tar,petroleum resins, rubber or other binder of hydrocarbon orhydrocarbonaceous origin.

The oil shale is present in an amount in the approximate range fromabout 5 to about 75 weight percent based on the hydrocarbonaceousmaterial. Amounts below the low end of this range are not now preferredbecause the advantages do notjustify the labor expense involved. Amountsabove the upper end of the range will yield per tanto the advantagesherein discussed. However, in some cases, too much loading will deny tothe composite sufficient of the properties of the binder. Thus, thoughwithin the broad scope of the invention amounts from about 0.5 to about95 weight percent are possible. for some applications, presentlypreferred, in all applications, if costs are disregarded, is a rangefrom about l() to about 60 weight percent of the hydrocarbonaceousmaterial.

In the manufacture of roofing shingles, the compounding of mastics,filling molded rubber products, producing paint pigments, masticcaulking and joint compound and the like, it has long been the practiceto use fillers for example, diatomaceous earth, limestone dust,asbestos, silica, slate, flour, clay and even Portland cement. Thesefillers, upon comparison to the oil shale powder of the invention, havebeen found to be inferior. It is now believed that the inferiority canbe attributed to the hydrophilic nature of these fillers. Thus, thesefillers usually have a moisture interface, due to moisture adsorbed onthe filler particles, when compounded with asphalt and this interface isthought to weaken the compounded structure, in many cases rendering itpermeable to air and water. Thus, we have found that by use of oil shalepowder, the major problem with fillers is overcome. Thus, oil shale isoleophilic and being so forms a tight bond with the hydrocarbonaceouscementing medium. Cut-back asphalt, for example, will form a continuousfilm on oil shale particles, i.e., it will oil-wet these particlescompletely, while other fillers, being more hydrophilic, will tend tobead or show observable contact angles under microscopic examination.The angle of wetting between asphalt and oil shale is appreciable largerthan whereas with other fillers this is often an acute angle, i.e., lessthan about 90.

Thus, we have found that durability of asphalt pavement can be greatlyenhanced by the use of oil shale filler, as herein described, sincecomplete coating of mineral fines can be obtained. This is rarely thecase with othe commonly used fillers for example, limestone, slate,flour, silica, etc.

Although there have been here stated the reasons for which thecompositions of the invention are thought to be unique in their makeupand properties, it is also possible that in the intense mixing procedureof the method of the invention whereby the carbonaceous substance e.g.the asphalt cement and oil shale powder are composited, there is aphysical and/or chemical action or interaction peculiar to the choice ofsubstances and their preparation prior to the compositing step.

Thus, it is known that the kerogen in the oil shale can be removedtherefrom by retorting. It is contemplated that in the mixing step orpossibly even in the grinding of the oil shale step, temperaturespermitting the release of some of the kerogen in a form such that thecompositing is made more tenacious occurs.

In any event, it does appear as a result of testing of properties thatthere is some action taking place between the oil shale powder and thebinder material with which it is composited since the properties cannotbe accounted for merely upon the basis of pure nonreacting physicaladmixture.

There is also to be considered the contact angles which result betweenthe oil shale and binder material respecting the exclusion of water notonly at the time of the intense or intimate admixture of the oil shalepowder and the binder material but also thereafter.

lt is an object of this invention to provide a hydrocarbonaceoussubstance-oil shale composition. lt is another object of this inventionto provide a method for compositing a hydrocarbonaceous substance orbinder material having the nature of asphalt, pitch, and the like, withan oil shale. lt is a further object of this invention to provide acomposition suitable for use in pavement, roofing materials, asphalttile, mastic, caulking, etc. It is a further object of this invention toimprove the aging, plasticity, covering and adhesion properties ofbinder materials.

Other aspects, concepts, objects and the several advantages of theinvention are apparent from a study of this disclosure and the appendedclaims.

According to the invention, there is provided a composite of ahydrocarbonaceous binder material as herein described and oil shale.Still according to the invention there is provided a method forcompositing a binder material as herein described with an oil shale 5which comprises the steps of grinding the oil shale to an averageparticle size of less than about 75 microns and then intimately admixingthe powder thus obtained with the binder material.

Generally, according to the now preferred forms of the invention, thehydrocarbonaceous binder materials which can be used and which can beimproved thereby include bituminous cements such as those prepared fromresiduals, pitch. Trinidad asphalt, etc.

The following table, by way of example, gives the pel5 troleum asphaltcements properties which are now preferred for such cements.

The selection of the asphaltic cement will depend on its application asis well known in the art. For example for road surfaces, the petroleumasphalt cement is a material having a penetration of from 75 to about100 and a ring and ball softening temperature of from about 40 to 65C.

Thus also for bituminous or asphalt roofing shingle production an airblown asphalt having a ring and ball softening point of about 93C. and apenetration of about 16-20 is preferred.

The nature and amount of binder material and oil shale to be used willvary widely depending upon the ultimate properties sought to be obtainedand can be determined by mere routine testing in the light of thisdisclosure.

The oil shale will contain usually from about 15 to about 40 gallons ofoil per ton of shale, preferably from about 25 to about 35 gallons ofoil per ton of shale.

In actual practice of the invention, the oil shale is ground to a propermesh size, usually 200, in a suitable apparatus such as a ball mill.

In the following are given physical characteristics and particle sizedistribution for six mineral fines, including the oil shale used in thisapplication.

Oil Shale fines have dolomite and calcite crystals as the main mineralconstituents. Kerogen, a bitumi' nous material, is present but difficultto distinguish optically. The minor components are albite, a type oftrielinic sodium feldspar, and illite. lllite particles are small thinflakes without a definite outline. The appearance is moderately angularwith a lamellar positioning noted with some particles.

Regular Shale fines are characterized by the calcite and quartz crystalsintermixed with a large number of muscovite mica crystals. The micacrystals are flat, thin and elastic. A minor constituent is kaolinite, ahydrous aluminum silicate clay.

Diatomaceous Earth fines consist of the silicon dioxide skeletalstructures of diatoms. The silica is mainly amorphous opal. Some quartzparticles are evident. The diatom structures are greatly varied in shapebut relatively uniform in size. The fragments present an interestingassortment of rods, perforated plates, and other configurations. Theparticles obviously would defy close packing or orientation.

Rhyolite fines show the major components are potassium feldspar andquartz. There is a small amount of biotite mica. The particles areirregular and less blocky. There is more uniformity in the generalappearance. Many ragged edges and nodules are apparent.

Slate fines consist of fine quartz crystals and muscovite mica as themajor components. Minor constituents are chloride and calcite. Theparticles are angular for calcite and flat for mica. Shapes areirregular.

Portland Cement is entirely calcium silicates. The particles are angularwith ragged, irregular shapes.

Constituent Analysis Determined by Emission Spectrograph and X-rayDiffraction Equipment Oil Reg. Diatom. Portland Shale Shale EarthRhyolite Slate Cement Chemical Parts per million Chromium Cr 300 270 3740 200 Vanadium V 37 I40 Nickel Ni l8 l7 l8 l8 l8 Barium Ba 69 690 690690 Boron B 'D D D D D D Phosphorus P 600 600 Iron Fe 4X10" 93 l0 IQX l04X10 19x10" 4 l0" Manganese Mn 310 310 3,000 310 300 300 Magnesium Mg 2ll0" 46 l0-' 5X10" SXIO SXIO" 5 ltf Lead Pb 34 60 Molybdenum Mo D D TinSn 15 Calcium Ca 2 I0" 35x10" 5Xl0'-' l-=l l0 ZXIO' 5X10 Cadmium Cd D DCopper Cu 70 44 4.000 70 200 70 Cobalt Co D Titanium Ti 19.000 l 9,0002.700 19,000 2,700 l9 ()00 Zirconium Zr l 600 690 Sodium Monoxide Na O4X10 2X10 2X10" 4X10" 4X10 D Aluminum Oxide Al- ,O;, 15x10" l5 l0 8X10"l4 l() l4 l0 lSX l0 -continued Constituent Analysis Determined byEmission Spectrograph and X-ray Diffraction Equipment Oil Reg. Diatom.Portland Shale Shale Earth Rhyolitc Slate Cement Chemical Parts permillion Silicon Oxide SiO 80x10" 54 l0' 8X10 54x10 8X10 8X10 DDctcrminedas present but not measured.

Percentage of Particles Smaller Than Indicated Size Size. Oil Reg.Diatom. Portland Microns Shale Shale Earth Ryolite Slate Cement 0.7 0.301.79 1.20 0.26 2.18 0.29 1.0 0.98 5.64 3.88 1.04 6.24 0.98 2 4.18 15.3712.95 4.11 1 .53 3.44 4 10.95 30.39 29.95 9.95 38.47 5.65 7 18.08 47.4048.15 16.06 54.60 8.20 10 22.75 56.67 56.96 20.04 61.54 10.93 40.3377.08 96.35 37.29 75.69 23.71 40 70.37 94.05 99.96 73.19 91.64 63.55 7095.89 99.52 100 98.56 99.41 96.27 75 l ()0 I01) 100 I00 lOO Thefollowing tabulations give additional information with respect tocompositions according to the inventhis ratio except diatomaceous earthwhich was blended to a 22:78 fines to asphalt ratio. This was betion.The tabulations are self-explanatory. 25 cause the high surface area ofthe diatomaceous earth required more asphalt for testing. Unlessotherwise indicated these compositions were used throughout the T$ OFRAW SHALE tests in this application.

SC Cf S5Lly ll OI per ton i Mm CO2 WW1 17 I The aging behavior andviscosity slope of compos- Ash. Wit/71 66 30 ited asphalt are propertiesfrom which the suitability of gg t: y the asphalt can be determinednormally. The following I 7 l I fi g q 2 is given to permit propertycomparisons of the several PROPERTIES OF REFERENCE indicated materials.The lower the slope value, the bet- ASPHALT ter the product properties,eg a low slope means low Penetration. 77 F. 100g. 5 sec. 92 d i SpecificGravity 60/60 10084 ten ency to lose plasticity and thus to becomebrittle or Softening Point. Ring & Ball. F. l l3 frangible.

Ductility. 77F.. 5 cm/min. 150+ l 'a AGING BEHAVIOR AND viscosiTY SLOPEViscosity. centistokes. 275 F. 340

l ils y vT Test 3 The aging apparatus continuously measures the visi v Iv 4 pcnutrmiom 100g 5 sac cosity of a test specimen at a controlledtemperature Retained Penetration. p j 64 while exposing a changing filmof asphalt (containing Ducti1ity.77F.. 5 cm/min. 150+ f. l d I i h. hviscosim centistokes 444 ines to a simu ate aging situation. n t istest. t e 325F. 136 specimens were aged for 24 hours at 325F. Viscosityis g fgg iff measured in centistokes centipoises density.

SURFACE AREA OF MINERAL FINES (PASSING 200 MESH Slope is the rate ofChange in viscosity during aging SIEVE) over a set time period. It iscalculated by dividing the Dccrmncd hY absmpm Surface Area numericaldifference in initial viscosity and final viscos- Mineral S M/Gram ityafter aging by the number of hours of aging, in this Oil Shale 2.3 caseby 24.

Reference Asphalt Compositions Containing:

Viscosity. Reference Regular Diatomaceous Portland Ccntistokes AsphaltOil Shale Shale Earth Rhyolite Slate Cement initial 139 350 310 410 315320 350 After 12 Hr. 158 370 365 455 400 360 435 After 24 Hr. 1x2 400425 500 4x0 410 490 Slope After 24 Hr. 1.79 2.08 4.79 3.75 6.88 3.755.83

Regular Shale 11.7 Dlutolhucuous Earth As shown above, the oil shalefilled asphalt hasthe glzyglltc lowest slope value of the filledasphalts and is therfor Portland Cement 1.7 least susceptable to becomebrittle upon aging.

Samples were prepared by stirring together in a 600 ml beaker 198 g oftest times with 252 g of the reference asphalt heated to 350F. The ratioof fines to asphalt is 44:56 percent by weight. All samples were blendedto WEATHEROMETER TEST The tests were carried out in a weatherometercabinet equipped with two carbon lamps to provide light and heat, and arotating element containing the sample holders. The element rotatesclockwise at the rate of one revolution per minute. Each sample holderrotates 60 counter-clockwise per one-half revolution of the element.During a two hour cycle, the samples are exposed to 102 minutes of lightat 140F. and 18 minutes of light and water spray at 8095F.

Glass plates 3 /2 X 3%; inches were used to hold the film. A sample ofasphalt blended with fines, in the ratios given previously, was placedon the glass plate to provide a film of about 3/32 inch averagethickness. The samples were weighed before and after exposure at roomtemperature.

Samples were weathered for 300 hours which is equivalent to 1 yearexposure.

From the weatherometer test results given below, it is evident that theoil shale filled asphalt had the lowest weight loss indicating goodadhesion of the asphalt to the filler and good cohesion of the asphaltfilm so that the particles are not readily detached and removed underthe test conditions.

Weight Loss After Weight gain. This sample was heated in an oven for 24hours at 140F. but weight gain remained constant.

Plastic properties, i.e., plasticity of the reference as- ADHESIONBEHAVIOR One of the important and unique characteristics of thecomposition according to the invention is adhesion. The followingadhesion tests were made with specimens prepared as described withresults as tabulated.

Test specimens were prepared by use of a brass mold 3/8 inch [.D. X l/2inch high. Reference asphalt was blended /50 by weight with Stoddardsolvent to produce the desired viscosity for handling at roomtemperature. The mineral fines in the same ratios as before were mixedwith the test asphalt solution to produce a composite in which theparticles were completely coated and the mixture of proper consistencyfor molding. The specimen was extruded from the mold into a dryporcelain dish without removing the solvent.

Distilled water at room temperature was added immediately to the dishcontaining the molded specimen until the specimen was completelyimmersed. Observations were made of the soaking reaction within 15minutes and after soaking 24 hours; a rating system was utilized havingthe following values:

0 Very Poor. Specimen disintegrated.

l Poor. Maintained form. Particles and asphalt separated substantially.2 Fair. Maintained form. Particles and asphalt showed some separation. 3Good. Slight discoloration but no visible separation. 4 Excellent.Particles completely coated with asphalt and no discoloration orseparation. Under this system a specimen was considered a failure unlessit rated 3 or 4 after soaking 24 hours.

Oil Regular Diatomaceous Portland Reference Asphalt Plus Shale ShaleEarth Rhyolite Slate Cement Without Additive 4 3 3 (l 3 0 With 17!Anti-strip 4 2 With l'7r' Hydrated Lime 0 Anti-strip & Hydrated Lime"The anti-strip additive was a l'att acid amine in a hydrocarbon\ehicle. a brownish liquid. density 0.932. pour point 45F. and a SayholtUniversal Second viscosity at 145F. of 269. (Pa\'ehond" (arlisleChemical Co.)

phalt, earlier described, composited with the indicated materials asbefore are given in the following table.

PLASTlC PROPERTIES: Test run in accordance with ASTM D-423 and D-424.

Liquid Plastic Plasticity Asphalt With Limit Limit Index Oil Shale 35.53l.l 4.4 Regular Shale 32.3 22.4 9.) Diatomaceous Earth I081) 103.2 4.8Rhyolite 25.3 23.3 2.0 Slate 29.9 22.4 7.5 Portland Cement l8.(1 18.0 (m

Oil Shale filler is shown to perform outstandingly compared to all otherfillers tested, having a rating of excellent without additive treatment.

The blank spaces in the table signify no additional benefit was foundafter the indicated treatment.

TENSILE AND SHEAR TESTS Finally. the tensile and shear test strengths ofspecimens which were prepared further illustrate the propertiesobtainable with the compositing of the ingredients of the invention.

Specimens were prepared by blending fines with reference asphalt at theratio of 44/56 weight percent except for diatomaceous earth which wasblended 22/78 as set forth previously. A special jig was used to providea film thickness of microns between test plates of /4 square inch area.Tests were conducted at 39.2". 77, and l l()F. for unaged and afteraging 24 hours at 325F. Specimens were pulled at a constant rate. Loadto failure was measured in pounds with a proving ring connected torecording equipment. Shear test was made with same equipment except fora special sample holder used to permit positioning at a right angle todirection of pull.

LOAD lN POUNDS REOUlRED FOR FAILURE 39.2F. 77F. 1 10F.

NA A NA A NA A TENSlLE Reference Asphalt 115 l 19 68.0 80.0 1 3 8.8Reference Asphalt Containing Oil Shale 208 262 60.9 75.8 8.8 120 RegularShale 249 259 47.8 67.9 9.0 14.2 Diatomaceous Earth 261 317 49.0 75.96.4 l 1.6 Rhyolite 260 212 32.2 62.2 9.1 12.9 Slate 287 333 61.8 81.87.7 15.2 Portland Cement 280 217 51.5 65.9 6.7 13.5 Average of FilledAsphalt 257.5 250 55.3 7l .6 7.95 13.2 SHEAR Reference Asphalt 1 17 13216,8 29.7 0 95 2 8 Reference Asphalt Containing Oil Shale 162 176 32.037.4 2.2 3.3 Regular Shale 172 182 27.3 32.5 31 4.7 Diatomaceous EarthI53 I91 27.] 34.9 2.2 3.0 Rhyolite 155 170 25.5 31.0 2.6 3.2 Slate 152170 24.3 37.7 3.0 3.2 Portland Cement 151 170 22.9 37.7 1.9 2.7 Averageof Filled Asphalt 157.5 I76 26.5 35.2 2.5 3.35

NA-Nonaged. A-Aged 24 hours at 325F. "Filler to asphalt ratios aredisclosed previously.

As shown by the test results, all the fillers tested show the expectedreinforcing properties, especially in the shear tests. The oil shalefiller performed well especially after aging and at the highertemperatures. Thus the advantages shown in the other tests have beenachieved without affecting the other desirable properties of a filler.

The oil shale which has been described and any oil shale which issuitable for the practice of the invention is one which when comminutedwill not become sticky to an extent such that comminution and/orcompounding or compositing cannot be accomplished therewith. Thus, ifthe oil shale releases too much oil during the grinding or crushing toaccomplish the desired particle size, it will, of course. not bepreferred according to the best mode of operation of the invention.Further, if 40 there is too little oil in the oil shale, it likely willhave a lower binding power and therefore would not be suitable.

When a rubber. or similar material is used, incorporation of thepowdered oil shale can be accomplished as in a rolling mixer or Banburymixer. Or the powdered oil shale may be added to a solution of therubber. After thorough mixing. the solvent is evaporated leaving ahomogeneous blend of oil shale and rubber.

The fillers herein discussed are to be distinguished from aggregate suchas crushed rock of fairly large size relative to the particle size ofthe subdivided shale.

In preparing a mixture of asphalt and oil shale filler according to theinvention either before or after aggregate has been added the desiredproportions are fed into, say, a pug mill in the absence of a solvent toobtain a free flowing composite which will have a temperature of theorder of several hundred degrees of Fahrenheit usually about 250 to375F. On cooling, the mass will set to a plastic which on curing for,say, 12 to 48 hours will harden. Slurry or emulsion mixing can be used.if desired.

It will be noted that the viscosity slope given in the table herein islower for the oil shale than for regular shale or the other materials ofthe table. Thus, the viseosity increase with accelerated aging. whichcauses brittleness in pavement or roofing, which is not desired. is muchless with oil shale filled with asphalt than for any of the other listedmaterials. This is due to the characteristics inherent in the oil shaleand in the composite of the invention as discussed elsewhere herein.

Any type of asphaltic material will benefit from the use of theinvention when a filled asphalt cement is required. Although the rangesof 0.5 to weight percent based on the asphalt, preferably 10-60 weightpercent. which are approximate ranges, have been given it will beobvious to one skilled in the art working with his knowledge and theinformation of this disclosure that in any case he can by mere routinetest determine other proportions with regard to specific binders andspecific oil shales to obtain best results in such specificcombinations. Thus, the actual amount required will depend on the enduse, the properties desired and will be well within the skill of thepractitioner and the standards known in the industry.

Thus, the broad range of 15 to 40 gallons of oil per ton of oil shalepreferably 25 to 35 gallons of oil per ton of oil shale given herein areapproximate ranges in which the best results of the invention can beobtained. One skilled in the art in possession of this disclosure willbe in position to suitably and routinely test for the specific oil shaleand binder and results or properties desired to determine the specificingredients and amounts which he should use.

Finally, on the particle size of the oil shale it is a requirement ofthe invention that the average particle size be of the order asindicated. Certain considerations obtain: It is necessary to have apowder that is not so fine as to make mixing difficult. Further, theflow of the mixed materials and curing will, of course. depend upon therelative sizes of the ingredients being ad mixed. The energyrequirements for admixing of the ingredients of the composition willdiffer to some extent depcnding upon particle size. condition of theingredients, etc. as one skilled in the art in possession of thisdisclosure can readily appreciate.

Although the invention is now preferably executed without use of anysolvent. it is within the scope of the invention during mixing of theingredients to apply heating and/or cooling methods and even a minorquantity of a wetting agent or solvent although this is 1 1 not nowpreferred in view of results obtained without such agents.

In summary, the data herein presented show:

The compositions with oil shale of this invention have superiorviscosity slopes, aging characteristics and adhesion than conventionallyused fillers. These advantages are gained without affecting the otherproperties such as tensile and shear strengths which vary only slightlyfrom one filler to the other.

The advantages gained by the use of the compositions of this inventionare improved durability of roads, roofs, etc., greater resistance tofreeze-thaw cycles because of greater water repellency and improved longterm viscosity stability, i.e., less likelihood of cracking or spalling.In addition, the strength of the asphaltic eement interfaces of filmwith the aggregate which is required for a pavement structure, will bebenefited by the improved adhesion of the asphalt film to the fillerparticle because of greater wettability of the particle by the asphalt.

Reasonable variation and modification are possible within the scope ofthe foregoing disclosure and the appended claims to the invention theessence of which is that a finely subdivided oil shale or powder uponadmixture with a binder as herein described and in manner and about asherein described has yielded compositions having superior propertiesalso as described.

We claim:

1. A bituminous binder comprising an asphalt compounded with finelysubdivided oil shale containing from about 15 to about 40 gallons of oilper ton and having a particle size of the order of less than about 75microns at a temperature in the approximate range 250-375F and the oilshale being present in an amount in the approximate range 0.5-95 weightpercent of the asphaltic material, said substance having better agingand adhesion properties than obtained when a conventional mineral filleris substituted for the particulate oil shale.

2. A composition according to claim 1 wherein the oil shale is presentin an amount in the approximate range 5 75 weight percent based on theasphalt.

3. A composition according to claim 1 wherein the oil shale is presentin an amount in the approximate range 10-60 weight percent based on theasphalt.

- 4. A composition according to claim 1 wherein the asphaltic materialhas the properties: Penetration (ASTM D 946) from about 16 to about 300;and Ring and Ball Softening Temperature (ASTM D 36) about 30 to about105C. and a Ductility at 77F. (ASTM D l 13) of a minimum about 3centimeters.

5. A composition according to claim 1 wherein the asphaltic mat is apetroleum asphalt.

6. A composition according to claim 5 wherein the petroleum asphalt hasa penetration, as herein defined, of about -100 and about 4065C. Ringand Ball Softening Temperature.

7. A composition according to claim 5 wherein the petroleum asphalt hasa penetration, as herein defined, of about 16-20, a Ring and BallSoftening Temperature of 80-105C. and a minimum ductility of about 3.

8. A composition of a petroleum asphalt having a penetration of about16-300 (ASTM D 946), and Ring and Ball Softening Temperature of fromabout 30 to about 105C.; and a Ductility at 77F. (ASTM D 113) of atleast about 3 centimeters in an admixture with about 0.5- weight percentbased on the asphalt of a finely subdivided oil shale having a particlesize of less than about 75 microns and containing about 15-40 gallons ofrecoverable oil per ton of shale, the oil shale being present in anamount in the approximate range 5-75 weight percent of the petroleumasphalt cement and being compounded with the asphalt at a temperaturebelow 375F.

9. A method for preparing an improved bituminous binder having betteraging and adhesion of properties than obtained with similar amounts ofsimilar sized mineral fillers which comprises bringing together underintense mixing conditions the ingredients of claim 1 in absence of asolvent at a temperature in the approximate range 250-375F, the oilshale being present in an amount in the approximate range 5-75 weightpercent of the asphalt and containing from about 15 to about 40 gallonsoil per ton of oil shale.

UNITED STATES PATENT AND TRADEMARK OFFICE QE'HFIQATE OF CORRECTIONPATENT N0. 3,902 ,914

DATED 1 September 2 19 75 KNV-ENTOMS) 3 Duane W. Gagle Homer L. Draperii is ceriified that error appears in the above-identified patent andthat said Letters Patent are hereby eorreciez as shown below:

Column 12 claim 4 line 7 before "about" insert from line 9 before"about" insert of Column 12 claim 5 line 11, delete "mat" and inserttherefor material Signed and Sealed thisthirtieth D f March 1976 [SEAL]Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParentsand Trademarks

1. A BITUMINOUS BINDER COMPRISING AN ASPHALT COMPOUNDED WITH FINELYSUBDIVIDED OIL SHALE CONTAINING FROM ABOUT 15 TO ABOUT 40 GALLONS OF OILPER TON AND HAVING A PARTICLE SIZE OF THE ORDER OF LESS THAN ABOUT 75MICRONS AT A TEMPERATURE IN THE APPROXIMATE RANGE 250*-375*F AND THE OILSHALE BEING PRESENT IN AN AMOUNT IN THE APPROXIMATE RANGE 0.5-95 WEIGHTPERCENT OF THE ASPHALTIC MATERIAL, SAID SUBSTANCE HAVING BETTER AGINGAND ADHESION PROPERTIES THAN OBTAINED WHEN A CONVENTIONAL MINERAL FILLERIS SUBSTITUTED BY THE PARTICULATE OIL SHALE.
 2. A composition accordingto claim 1 wherein the oil shale is present in an amount in theapproximate range 5 - 75 weight percent based on the asphalt.
 3. Acomposition according to claim 1 wherein the oil shale is present in anamount in the approximate range 10-60 weight percent based on theasphalt.
 4. A composition according to claim 1 wherein the asphalticmaterial has the properties: Penetration (ASTM D 946) from about 16 toabout 300; and Ring and Ball Softening Temperature (ASTM D 36) about 30*to about 105*C. and a Ductility at 77*F. (ASTM D 113) of a minimum about3 centimeters.
 5. A composition according to claim 1 wherein theasphaltic mat is a petroleum asphalt.
 6. A composition according toclaim 5 wherein the petroleum asphalt has a penetration, as hereindefined, of about 75-100 and about 40*-65*C. Ring and Ball SofteningTemperature.
 7. A composition according to claim 5 wherein the petroleumasphalt has a penetration, as herein defined, of about 16-20, a Ring andBall Softening Temperature of 80*-105*C. and a minimum ductility ofabout
 3. 8. A composition of a petroleum asphalt having a penetration ofabout 16-300 (ASTM D 946), and Ring and Ball Softening Temperature offrom about 30* to about 105*C.; and a Ductility at 77*F. (ASTM D 113) ofat least about 3 centimeters in an admixture with about 0.5-95 weightpercent based on the asphalt of a finely subdivided oil shale having aparticle size of less than about 75 microns and containing about 15-40gallons of recoverable oil per ton of shale, the oil shale being presentin an amount in the approximate range 5-75 weight percent of thepetroleum asphalt cement and being compounded with the asphalt at atemperature below 375*F.
 9. A method for preparing an improvedbituminous binder having better aging and adhesion of properties thanobtained with similar amounts of similar sized mineral fillers whichcomprises bringing together under intense mixing conditions theingredients of claim 1 in absence of a solvent at a temperature in theapproximate range 250*-375*F, the oil shale being present in an amountin the approximate range 5-75 weight percent of the asphalt andcontaining from about 15 to about 40 gallons oil per ton of oil shale.